Moldable article of glass fibers and a modified phenolic binder

ABSTRACT

A moldable article comprising a woollike mass of intermeshed glass fibers bonded to one another at points of contact by a phenolic binder. The binder is substantially dry and curable, and comprises from 40 percent to 91 percent of a curable phenolformaldehyde condensate, from 4 percent to 40 percent of urea and from 5 percent to 45 percent of dicyandiamide. Preferably, the binder additionally contains a thickening agent, as well as a siloxane or other release agent and emulsified petroleum oil to minimize sticking and resin build-up during molding of the article.

United States Patent Appl. No. Filed Patented Assignee MOLDABLE ARTICLEOF GLASS FIBERS AND A MODIFIED PHENOLIC BINDER 14 Claims, No DrawingsU.S..Cl 161/170,

65/4, 117/126GR,156/l67, 156/335, 260/172, 260/293, 260/515, 264/136Int. Cl D04h 3/12, C08g 5/00 Field of Search 161/170;

65/3.4; 156/167, 335; 260/172, 29.3, 838, 840, 51.5; 117/161 L, 126GR;264/136 Primary Examiner-Robert F. Burnett Assistant Examiner-Linda M.Carlin Att0rneys-Staelin & Ovcrman and Thomas R. Schuman ABSTRACT: Amoldable article comprising a woollike mass ofintermeshed glass fibersbonded to one another at points of contact by a phenolic binder. Thebinder is substantially dry and curable, and comprises from 40 percentto 91 percent of a curable phenol-formaldehyde condensate, from 4percent to 40 percent of urea and from 5 percent to 45 percent ofdicyandiamide. Preferably, the binder additionally contains a thickeningagent, as well as a siloxane or other release agent and emulsifiedpetroleum oil to minimize sticking and resin build-up during molding ofthe article.

MOLDABLE ARTICLE OF GLASS FIBERS AND A MODIFIED PIIENOLIC BINDER Thisapplication is a continuation-in-part of my copending application Ser.No. 783,432 filed Dec. l2, I968 and now abandoned.

BACKGROUND OF THE INVENTION Various articles comprising a woollike masswith intermeshed glass fibers and a phenolic binder have been known forsome time, and have been used, for example, in the production of moldedpipe insulation and automotive crash pads. The previously known moldablearticles of the indicated type, however, have had comparatively shortstorage lives because cure of the binder proceeded at a relatively rapidrate, even under ambient conditions. In addition, such articles havebeen difficult to handle because the binder was a viscous, tacky liquidwhich adhered to itself and to other articles, e.g. interleaving in aroll. Finally, molding of such articles was difficult and time consumingbecause resin buildup in matched molds occurred to such an extent, afteronly a few hours of molding, that detail of the mold was not reproducedin the final article. As a consequence, molds had to be cleanedfrequently.

THE PRESENT INVENTION The instant invention is based upon the discoveryof an improved binder for a moldable article comprising a woollike massof intermeshed glass fibers and a binder. The improved binder comprisesa phenol-formaldehyde condensate, urea and dicyandiamide. The urea anddicyandiamide are present in the binder in such proportion that thebinder, when dehydrated, is stable at 100 F. for at least 1 month, andthe proportion of dicyandiamide is sufficiently high to increase theviscosity and to cause a substantial reduction in the tack of thebinder. Preferably, the binder additionally contains an amount of atleast one thickening agent sufficient to increase the viscosity, bodyand film strength thereof, and a siloxane or other release agent and anemulsified petroleum oil.

OBJECTS It is an object of the invention to provide an improved moldablearticle comprising a woollike mass of intermeshed glass fibers bonded toone another at points of contact by a substantially dry, curable,phenolic binder.

lt is a further object of the invention to provide such a moldablearticle wherein the binder comprises a phenol-formaldehyde condensate,urea and dicyandiamide.

It is still another object of the invention to provide such a moldablearticle wherein the binder additionally contains a' EXAMPLE I A phenolicbinder for use in producing a moldable article according to theinvention was produced in an agitated, 1000- gallon, jacketed, steelmixing kettle. The following ingredients were used to produce thebinder: water, as required, Silane A* subseqcuntly described. 5 3/5pounds, ammonium sulfate l8 pounds, urea I80 pounds, dicyandiamide I76pounds Thickening Agent B 9.] pounds, bone glue 89 pounds, ammoniumhydroxide, in required, Phenolic Resin C I074 pounds, and SlliconeRelease Agent D 26 3/5 pounds.

The mixing kettle was first charged with 175 gallons of water, andagitation was then commenced, and was continued until production of thebinder was complete. Steam was then circulated through the jacket of themixing kettle until the water therein reached a temperature of F. TheThickening Agent B was then added sufficiently slowly to preventlumping. Fifteen minutes after the addition of the Thickening Agent Bwas complete, the Silane A, the ammonium sulfate, the urea and thedicyandiamide and water, as required to bring the volume in the mixingkettle to 370 gallons, were added and steam was circulated in the jacketto bring the temperature of the partial charge to I30 F. The bone gluewas then added to the mixing kettle, and steam was circulated throughthe jacket, as required, to maintain the temperature of the partialcharge at 130 F. until a uniform dispersion substantially free of lumpsand particles was obtained. A pH adjustment was then made by addingapproximately 3 gallons of 28 percent 6 The terms percent and parts" areused herein and in the appended claims to refer to percent and parts byweight, unless otherwise indicatedammonium hydroxide, and the PhenolicResin C was then added, together with a total of approximately 9additional gallons of 28 percent ammonium hydroxide. The pH of thebinder was checked periodically during the addition of the PhenolicResin C, and the total amount of ammonium hydroxide used was thatnecessary to provide a pH of 8.5 after completion of the addition of thePhenolic Resin C. The Silicone Release Agent D was then added to themixing kettle, followed by water, as required to provide a total of 500gallons. The complete binder was then agitated for an additional l5minutes, and was used as described below to produce a moldable articleaccording to the invention.

The binder, produced as described above, was sprayed into a forming hoodthrough which newly-formed glass fibers were being projected downwardlyonto a foraminous conveyor so that a woollike mass of intermeshed glassfibers with associated binder was collected on the conveyor. Theproportion of binder to glass fibers was adjusted so that the binder, ona dry solids basis, constituted approximately 17 percent of the totalweight of fibers and binder. The nominal diameter of the specific fibersused in this procedure was twenty-six hundred-thousandths of an inch. Avacuum box was used under the conveyor in the forming hood to facilitatedeposition of the fibers and associated binder, and, also, to aid inevaporating some of the moisture from the binder. The woollike mass, ascollected on the foraminous conveyor, was at a temperature of about F.It was then conveyed through an unheated oven at an ambient temperatureof about 75 F and in which it cooled, in a period of approximately 5minutes, to a temperature of about 130 F. Upon emergence from theunheated oven, the woollike mass was sensibly dry (moisture content ofabout 1% percent), and the binder was a substantially non- ,tacky solid.The woollike moldable article was then compressed to an apparent densityof about 10 pounds per cubic foot (original density about one-half poundper cubic foot and thickness about 4 we inches), and rolled with waxedpaper interleaving. Kraft paper may also be used.

Silane A had the formula:

Thickening Agent B is composed of approximately 1 part of locust beangum and l part of a xanthomanas hydrophilic colloid. Xanthomanashydrophilic colloid is a biosynthetic polysaccharide composed ofglucose, mannose and glucuronic acid in a molar ratio of 2:1 :1; thereis one acetyl group for approximately each one-fourth unit of thepolymer. Thickening Agent B is, therefore, a polysaccharide thickeningagent; it is commercially available under the designation Kelgum."

Phenolic Resin C was produced from 51.15 parts of 52 percentformaldehyde, 31 parts of phenol, 2.4 parts of barium oxide, l0.83 partsof water and sulfuric acid, as required. The formaldehyde and the phenolwere first charged into a suitable reactor and mixed. The barium oxidewas then dissolved in the water, and the resulting solution was chargedinto the reactor.

The reaction mixture was then heated for two hours at 100 F 1% hours at110 F., two hours at 125 F. and approximately 5 hours at 140 F. Thereaction mixture was cooled to 90 F. when the free formaldehyde contentthereof reached 4.6 percent, and sulfuric acid was then added to lowerthe pH to 7.3. Phenolic Resin C had a solids content of 45.5 percent,and a stroke cure of 115 seconds. Silicone Release Agent D wasessentially a methylpolysiloxane, with some ethyl groups; it iscommercially available under the trade designation UCY-S 287" orL-49.

Molded ceiling tiles have been produced from the moldable articleproduced as described in example 1. The tiles, approximately one footsquare, with opposed stapling tabs, and approximately one-sixteenth inchthick, were molded in matched dies of appropriate contour, maintained ata temperature of 525 F., using a molding cycle of 45 seconds. Themoldable article was merely unrolled, cut to approximate size andinserted in the mold; no difficulty was encountered in handling, becausethe article did not adhere appreciably to the interleaving, and becausethe cut mold charges were sufficiently rigid that they could be handledreadily without deformation and did not stick to one another in stacks.lt has been found that, on the average, 8,400 molding cycles can becarried out before there is sufficient resin build-up in a single moldto require cleaning thereof.

For purposes of comparison, a moldable article was produced generally asdescribed above, but using a binder composed of water, Silane A,ammonium sulfate, Phenolic Resin C and an oil emulsion, plus sufficientammonium hydroxide to bring the pH thereof to 8.5. The moldable articleproduced from this binder is difficult to handle because it sticks tointerleaving in a roll, and because stacks or precut mold chargesadhered to one another. In addition, the material is difficult to handlebecause it is limp and flufiy. Finally, resin build-up in molds is muchmore rapid, a maximum of about 4,800 cycles being possible before moldcleaning is necessary, even when the molds are pretreated with asilicone release agent before use and a polytetrafluoroethylene releaseagent is sprayed on the mold surfaces after approximately each moldingcycles.

1n the procedure described in example 1, above, the Phenolic Resin C,the urea and the dicyandiamide were all added separately to a mixingkettle in producing the binder. It has been found that all or a part ofthe urea and of the dicyandiamide can be combined with a phenolic resin,and can even be partially cocondensed therewith, so that all or a partof the urea and all or a part of the dicyandiamide can be combined withthe phenolic resin prior to formulation of a binder. An illustrativeprocedure for producing a moldable article according to the inventionwherein all of the urea and a part of the dicyandiamide are firstcombined with a phenolic resin, and the resulting combination is thenused in formulating a binder is described in example 2, below.

EXAMPLE 2 A phenolic binder for use in producing a moldable articleaccording to the invention was produced as described in example l,above, from 45 ounces of Silane A, 8% pounds of ammonium sulfate, 80pounds of dicyandiamide, 4% pounds of Thickening Agent 8, 50 pounds ofbone glue, 64 gallons of Phenolic Resin E, 15% pounds of SiliconeRelease Agent B, water sufficient to make a total of 250 gallons andammonium hydroxide as required to adjust the final pH of the binder to8.5. Moldable articles were produced from glass fibers and the binderproduced as described in this paragraph hereof, and by the methodgenerally described in example 1, above. The resulting moldable articleswere found to be substantially equivalent to those produced as describedin example 1.

Phenolic Resin E was produced from 52 parts of 52 percent formaldehyde,27.3 parts of phenol, 8.2 parts of water, 4 parts of barium monohydrate,2.7 parts of dicyandiamide, 4.1 parts of urea, and sulfuric acid asrequired for a pH adjustment. The phenol, the formaldehyde and the waterwere first charged to a suitable, agitated reactor, and were heated fora total of 3 hours at F. The barium monohydrate was added stepwiseduring the first two hours of heating at 100 F. The temperature of thereaction mixture was then increased to F. and maintained thereat for 1%hours, and was then increased to F. and maintained thereat until the endof the cook cycle. When the free formaldehyde content reached 7.0percent, the dicyandiamide was added to the reaction mixture; one hourafter the start of the dicyandiamide addition, the urea was added and,30 minutes later, the reaction mixture was cooled to 100 F. and sulfuricacid was added, as required, to bring the pH to 7.2.

In the binders produced as described in examples 1 and 2, above, theSilicone Release Agent D was used for the purpose of minimizing resinbuild-up during a final molding step and also to facilitate removal ofthe molded article from the mold. Accordingly, this ingredient can beeliminated altogether whenever it is desired to carry out the finalmolding step in such a manner that resin buildup is not a problem, forexample, because temporary molds are used for only a few cycles, orbecause permanent molds which have been treated so that the resin doesnot adhere thereto are used. Where the release function is desired, ithas been found that various methyl polysiloxanes can be substituted forthe Silicone Release Agent D, for example those available under thedesignations DC-22, LE-46, LE-48, XF-11011A, and HV-490, the last beingan emulsion from 100,000 centistoke viscosity dimethylpolysiloxane. Ithas also been found that the monoethanolamide of ricinoleic acid can besubstituted for the Silicone Release Agent D, and with substantiallyequivalent results. The specific amide that has been used as a releaseagent had an acid value of 5, and iodine value of 80, a hydroxyl valueof 295, a saponification value of 15, a specific gravity of 1.000(25/25), a penetration hardness of 90 and a melting point of 40 C.

The bone glue and the Thickening Agent B in the binders produced asdescribed in examples 1 and 2 are both thickening or gelling agentswhich increase the viscosity, body and film strength of the binder. Suchthickening agents, or equivalents therefor, are preferably employed inbinders for producing moldable articles according to the invention.However, the urea and dicyandiamide in such a binder causesolidification upon substantial dehydration: even without a thickeningor gelling agent such moldable articles are significantly improvedbecause of greater stiffness and reduced tackiness by comparison withpreviously-known binders. Other thickening agents can be substituted forthe bone glue and for the Thickening Agent B specifically disclosed inexamples 1 and 2. While the optimum amount of the thickening agent orthickening agents depends upon the identity thereof, it usually rangesfrom about 2 percent to about 35 percent, based upon the weight of thephenol-formaldehyde condensate, urea and dicyandiamide, on a dry solidsbasis. Examples of other operable thickening agents include methylcellulose, alginates, gelatin and various acrylic-thickening agents,which may be emulsion polymers, solutions or dispersions.

Urea and dicyandiamide in a binder of an article according to theinvention also stabilize the binder at 100 F. for a minumum of one monthin the sense that satisfaction moldings can be produced from articlesaccording to the invention which have been maintained at 100 F. for onemonth. This is another respect in which an article according to theinvention is significantly superior to previously-known similar articleswhich would become useless for molding purposes afier only a few days at100 F.

It has also been found that a significant increase in the number ofmolding cycles performed before mold cleaning is required, can beattained by including in a binder of this invention an emulsifiedpetroleum oil along with a methylpolysiloxane such as Silicone ReleaseAgent D, described above and commercially available under the tradedesignation UCY -5287 or L-4Q. An illustrative procedure for formulatingsuch a binder is described in the following example 3.

EXAMPLE 3 A phenolicbinder for use in producing a moldable articleaccording to the invention was produced as described in example 1,above, from 6.75 pounds of Silane A, 27 pounds of ammonium sulfate, 634pounds of dicyandiamide, 9.3 pounds of Thickening Agent B, 1,899 pounds(solids) or 388 gallons of Phenolic Resin E, 103 pounds of an emulsifiedpetroleum oil, 26.7 pounds of Silicone Release Agent D, water sufficientto make a total of 1,500 gallons and ammonium hydroxide as required toadjust the final pH of the binder to 8.5. Moldable articles wereproduced from glass fibers and the binder produced as described in thisparagraph hereof, and by the method generally described in example 1,above. The resulting moldable article was found to be substantiallyequivalent to that produced as described in example 1.

Molded ceiling tiles were produced from the moldable article asdescribed in example 1. It was found that superior resistance to resinbuild-up in the molds was obtained using this example 3 formulation.After approximately 25,000 molding cycles of 40 to 60 second duration atabout 525 F. the molds were clean and shiny and exhibited no resinbuild-up.

The petroleum oil used in this formulation is commercially available asShell 230" and has a flash point higher than 585 F. The petroleum oilwas emulsified with a synthetic petrole urn sulfonate commerciallyavailable as Morpel X914" and an emulsifying agent commerciallyavailable as Triton X1 14. Emulsification of the petroleum sulfonate oilrenders it compatible with phenol-formaldehyde resin.

Any commercially available petroleum oil may be used so long as itsflash point exceeds the temperature attained during the molding cycleemployed; this, of course, prevents flashing offofthe oil during themolding step.

In its essential details, the instant invention comprises a moldablearticle which is a woollike mass of intermeshed glass fibers bonded toone another at points of contact by a substantially dry, curable,phenolic binder. The phenolic binder comprises from 40 percent to 91percent of a curable phenol-for maldehyde condensate, from 4 percent to40 percent of urea, and from 5 percent to 45 percent of dicyandiamide,based upon the total of phenol-formaldehyde condensate, urea anddicyandiamide. The proportion of urea dicyandiamide in the binder issufficiently high that the dehydrated binder is stable at 100 F. for atleast one month, and the proportion of dicyandiamide is sufficientlyhigh that the binder is substantially nontacky. The dicyandiamide makesthe binder substantially nontacky probably in part by virtue of itscrystallization. In general, the binder in a moldable article accordingto the invention can constitute from about 5 percent to about 45 percentof the weight of the article. The optimum percentage of the binderdepends upon fiber diameter and the physical properties desired. Ingeneral, the smaller the fiber diameter, the greater the proportion ofbinder required, and vice versa, because the amount of binder requiredis a function of the total fiber surface in the moldable article. Theapparent density of an article according to the invention, for example,when compression packaged, can vary substantially depending upon thedegree of compression, and usually ranges from about :a pound to about30 pounds per cubic foot. Preferably, the binder of an article accordingto the invention contains an amount of at least one thickening agentsufficient appreciably to increase the viscosity, body and film strengththereof; the thickening agent may constitute as little as one-fifthpercent or as much as 35 percent, depending upon its specific identityand preferably, particularly when the thickening agent is a combinationof bone glue and a polysaccharide, ranges from about 0.55 percent toabout 27 percent, in all cases based upon the total dry solids ofphenolic resin, urea and dicyandiamide.

Ideally, the binder in an article according to the inventionadditionally contains a release agent and an emulsified petroleum oil.The release agent is employed usually in an amount ranging from aboutonehalf percent to about 10 percent, based upon the total weight of thephenolformaldehyde condensate, urea and dicyandiamide;methylpolysiloxanes and the monoethanolamide of ricinoleic acid areexamples of ad vantageous release agents. The emulsified petroleum oilis used generally in an amount ranging from about 1 to 10 percent, basedupon the total phenol-formaldehyde condensate, urea and dicyandiamide.Preferred andoptimum proportions of binders for articles according tothe invention are set forth in table 1, below:

Preferably a resole, initial mole ratio of formaldehyde to phenol fromabout 2.5:] to about 3.5: 1.

"Based upon total of phenolformaldehyde, urea and dicyandiamide on a drysolids basis.

It will be apparent that various changes and modifications can be madefrom the specific details set forth herein without departing from thespirit and scope of the invention as defined in the appended claims.

What 1 claim is:

l. A moldable article comprising a woollike mass of intermeshed glassfibers bonded to one another at points of contact by a substantiallydry, curable, phenolic binder, said phenolic binder comprising from 40percent to 91 percent ofa curable phenol-formaldehyde condensate, from 4percent to 40 percent of urea and from 5 percent to 45 percent ofdicyandiamide, based upon the total of phenol-formaldchyde condensate,urea and dicyandiamide, the proportion ofurea and dicyandiamide in saidbinder being sufficiently high that the dehydrated binder is stable atF. for at least one month, and the proportion of dicyandiamide beingsufficiently high to increase the viscosity and to cause a substantialreduction in the tack of the-binder.

2. A moldable article as claimed in claim 1 wherein the binderconstitutes from about 5 percent to about 45 percent of the weight ofthe article.

3. A moldable article as claimed in claim 2 having an apparent densityfrom aboutone-half pound to about 30 pounds per cubic foot.

4. A moldable article as claimed in claim 3 wherein .the binder containsan amount of at least one thickening agent suft'icient appreciably toincrease the viscosity, body and film strength thereof.

5. A moldable article as claimed in claim 4 wherein the thickening agentcomprises from one-half percent to about 25 percent of a polysaccharide,based upon the total weight of phenol-formaldehyde condensate, urea anddicyandiamide.

6. A moldable article as claimed in claim 4 wherein the thickening agentcomprises from one-half percent to 25 percent of bone glue, based uponthe total weight of phenol-formaldehyde condensate, urea anddicyandiamide.

7. A moldable article as claimed in claim 6 wherein the thickening agentadditionally comprises from about 0.1 to about 1 percent of apolysaccharide supplemental thickening agent, based upon the totalweight of the phenol-formaldehyde condensate, urea and dicyandiamide.

7 IXEBIdEHie article as claimed in claim'5 wherein the binder includes,based upon the total weight of phenol-formaldehyde condensate, urea anddicyandiamide, from about 0.25 percent to about 3 percent of releaseagent effective to prevent adhesion between a heated mold surface andthe binder during cure of the latter in contact with the former.

9. A moldable article as claimed in claim 8 wherein the binder includes,based upon the total weight of phenol-formaldehyde condensate, urea anddicyandiamide, from about 1 percent to about percent of an emulsifiedpetroleum oil.

10. A moldable article as claimed in claim 7 wherein the binderincludes, based upon the total weight of phenol-formaldehyde condensate,urea and dicyandiamide, from about 0.25 percent to about 3 percent ofrelease agent effective to prevent adhesion between a heated moldsurface and the binder during cure of the latter in contact with theformer.

11. A moldable article as claimed in claim 8 wherein the release agentis selected from the group consisting of methylpolysiloxane fluids andthe monoethanolamide of ricinoleic acid,

12. A moldable article as claimed in claim 9 wherein the release agentis selected from the group consisting of methypolysiloxane fluids andthe monoethanolamide of ricinoleic acid.

13. A method of making a moldable article comprising the steps of:

a. forming glass fibers from molten steams of glass;

b. projecting said fibers toward a collecting surface;

c. introducing a curable phenolic binder into said projected fibers,wherein said phenolic binder comprises from 40 percent to 91 percent ofa curable phenol-formaldehyde condensate, from 4 percent to 40 percentof urea and from 5 percent to 45 percent of dicyandiamide, based uponthe total of phenol-formaldehyde condensate, urea and dicyandiamide;

d. depositing said projected fibers in association with said binder intoa woollike mass of intermeshed fibers on said collecting surface;

e. converting said binder associated with said woollike mass of fibersto a substantially nontacky, but uncured, state; and

f. associating said woollike mass with an interleaving material wherebysaid woollike mass can be stored, shipped or otherwise handled prior tomolding.

14. A method of making a molded article comprising the steps of:

a. forming glass fibers from molten streams of glass;

b. projecting said fibers toward a collecting surface;

c. introducing a curable phenolic binder into said projected fibers,wherein said phenolic binder comprises from 40 percent to 91 percent ofa curable phenol-formaldehyde condensate, from 4 percent to 40 percentof urea and from 5 percent to 45 percent of dicyandiamide, based uponthe total of phenol-formaldehyde condensate, urea and dicyandiamide;

d. depositing said projected fibers in association with said binder intoa woollike mass of intermeshed fibers on said collecting surface;

e. converting said binder associated with said woollike mass of fibersto a substantially nontacky, but uncured, state;

f. compressing said woollike mass to an apparent density of about 0.5 toabout 30 pounds per cubic foot;

g. cutting said woollike mass into the approximate size and shape of themolded article; and

h. molding said woollike mass with heated molding means a a temperaturesufficient to cure said binder to a hardened, infusible state andthereby produce the molded article.

2. A moldable article as claimed in claim 1 wherein the binderconstitutes from about 5 percent to about 45 percent of the weight ofthe article.
 3. A moldable article as claimed in claim 2 having anapparent density from about one-half pound to about 30 pounds per cubicfoot.
 4. A moldable article as claimed in claim 3 wherein the bindercontains an amount of at least one thickening agent sufficientappreciably to increase the viscosity, body and film strength thereof.5. A moldable article as claimed in claim 4 wherein the thickening agentcomprises from one-half percent to about 25 percent of a polysaccharide,based upon the total weight of phenol-formaldehyde condensate, urea anddicyandiamide.
 6. A moldable article as claimed in claim 4 wherein thethickening agent comprises from one-half percent to 25 percent of boneglue, based upon the total weight of phenol-formaldehyde condensate,urea and dicyandiamide.
 7. A moldable article as claimed in claim 6wherein the thickening agent additionally comprises from about 0.1 toabout 1 percent of a polysaccharide supplemental thickening agent, basedupon the total weight of the phenol-formaldehyde condensate, urea anddicyandiamide.
 8. A moldable article as claimed in claim 5 wherein thebinder includes, based upon the total weight of phenol-formaldehydecondensate, urea and dicyandiamide, from about 0.25 percent to about 3percent of release agent effective to prevent adhesion between a heatedmold surface and the binder during cure of the latter in contact withthe former.
 9. A moldable article as claimed in claim 8 wherein thebinder includes, based upon the total weight of phenol-formaldehydecondensate, urea and dicyandiamide, from about 1 percent to about 10percent of an emulsified petroleum oil.
 10. A moldable article asclaimed in claim 7 wherein the binder includes, based upon the totalweight of phenol-formaldehyde condensate, urea and dicyandiamide, fromabout 0.25 percent to about 3 percent of release agent effective toprevent adhesion between a heated mold surface and the binder duringcure of the latter in contact with the former.
 11. A moldable article asclaimed in claim 8 wherein the release agent is selected from the groupconsisting of methylpolysiloxane fluids and the monoethanolamide ofricinoleic acid.
 12. A moldable article as claimed in claim 9 whereinthe release agent is selected from the group consisting ofmethylpolysiloxane fluids and the monoethanolamide of ricinoleic acid.13. A method of making a moldable article comprising the steps of: a.forming glass fibers from molten streams of glass; b. projecting saidfibers toward a collecting surface; c. introducing a curable phenolicbinder into said projected fibers, wherein said phenolic bindercomprises from 40 percent to 91 percent of a curable phenol-formaldehydecondensate, from 4 percent to 40 percent of urea and from 5 percent to45 percent of dicyandiamide, based upon the total of phenol-formaldeHydecondensate, urea and dicyandiamide; d. depositing said projected fibersin association with said binder into a woollike mass of intermeshedfibers on said collecting surface; e. converting said binder associatedwith said woollike mass of fibers to a substantially nontacky, butuncured, state; and f. associating said woollike mass with aninterleaving material whereby said woollike mass can be stored, shippedor otherwise handled prior to molding.
 14. A method of making a moldedarticle comprising the steps of: a. forming glass fibers from moltenstreams of glass; b. projecting said fibers toward a collecting surface;c. introducing a curable phenolic binder into said projected fibers,wherein said phenolic binder comprises from 40 percent to 91 percent ofa curable phenol-formaldehyde condensate, from 4 percent to 40 percentof urea and from 5 percent to 45 percent of dicyandiamide, based uponthe total of phenol-formaldehyde condensate, urea and dicyandiamide; d.depositing said projected fibers in association with said binder into awoollike mass of intermeshed fibers on said collecting surface; e.converting said binder associated with said woollike mass of fibers to asubstantially nontacky, but uncured, state; f. compressing said woollikemass to an apparent density of about 0.5 to about 30 pounds per cubicfoot; g. cutting said woollike mass into the approximate size and shapeof the molded article; and h. molding said woollike mass with heatedmolding means at a temperature sufficient to cure said binder to ahardened, infusible state and thereby produce the molded article.